CN107394242A - A kind of preparation method of resistant to elevated temperatures amination graphene oxide/sulfonate polybenzimidazole proton exchange composite membrane - Google Patents
A kind of preparation method of resistant to elevated temperatures amination graphene oxide/sulfonate polybenzimidazole proton exchange composite membrane Download PDFInfo
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- CN107394242A CN107394242A CN201710578241.8A CN201710578241A CN107394242A CN 107394242 A CN107394242 A CN 107394242A CN 201710578241 A CN201710578241 A CN 201710578241A CN 107394242 A CN107394242 A CN 107394242A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
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Abstract
The invention belongs to fuel battery proton exchange film technical field, more particularly to a kind of preparation method of resistant to elevated temperatures amination graphene oxide/sulfonate polybenzimidazole proton exchange composite membrane.Under nitrogen protection by tetramine monomers, contain the non-sulfonated diacid monomer of O flexible groups, sulfonation diacid monomer and amination graphene oxide in-situ polymerization; prepare amination graphene oxide/sulfonate polybenzimidazole proton exchange composite membrane; composite membrane has good mechanical stability and heat resistance, and the purer sulfonate polybenzimidazole of its proton conductivity is greatly improved.
Description
Technical field
The invention belongs to fuel battery proton exchange film technical field, more particularly to a kind of resistant to elevated temperatures amination oxidation stone
The preparation method of black alkene/sulfonate polybenzimidazole proton exchange composite membrane.
Background technology
High temperature proton exchange film fuel cell can improve and simplify water management because it has faster Chemical Kinetics
System and the advantages that more efficient heat management and environmental resistance can be obtained as the study hotspot of current fuel cell.Proton is handed over
Change the operating temperature that film determines fuel cell as the core component of fuel cell its operating temperature, traditional Nafion membrane matter
Sub- conductive performance depends critically upon aqueous water, and its operating temperature can cause PEM to be dehydrated at 60~90 DEG C, when temperature is too high, proton
Electrical conductivity drastically declines, battery performance deep fades.Therefore under exploitation high temperature (>=100 DEG C) there is good proton conduction property
PEM turns into current hotspot.
Sulfonate polybenzimidazole (SPBI) has preferable proton conduction property, and still, sulfonic introducing reduces
SPBI mechanical stability and heat endurance, and sulfonated membranes must be fully hydrated to obtain higher proton conductivity.
The content of the invention
The technical problems to be solved by the invention are：PEM mechanical performance, heat endurance are poor, at high temperature easily
Dehydration causes proton conductivity to decline,
On the other hand, graphene oxide is introduced into SPBI matrix to improve the mechanical stability of composite membrane, thermostabilization by the present invention
Proton conductivity under property and high temperature.Graphene oxide (GO) has amphiphilic performance, and its flexible and highly stable structure can
To effectively improve the chemistry of composite membrane, heat and mechanical stability, meanwhile, GO is because containing-O- ,-OH and-COOH functional group energy
Enough attracting proton, proton can relatively easily pass through GO two-dimensional materials, and rise temperature can remarkably promote the process that proton passes through,
And GO has high-specific surface area, be advantageous to build continuous proton transfer passage, but GO easily reunites in itself, it is and organic molten
The compatibility of agent is bad, and irreversible precipitation of reuniting easily occurs, is limited so that the performance of proton exchange composite membrane improves
System, it is therefore necessary to GO is modified,
Therefore the triethylene tetramine of present invention good thermal stability is modified GO so as to introduce amino, modified GO is doped to
In SPBI matrix, compatibility is improved using the acid-base function of sulfonic group and basic amine group, the acid-base pair of formation supplies proton with anhydrous
Mode is quickly conducted, and so as to construct continuous anhydrous proton transfer passage, improves the proton conduction property of composite membrane at high temperature,
Meanwhile the present invention prepares amination graphene oxide/sulfonate polybenzimidazole using situ aggregation method, by amination
Graphene oxide is distributed in polymer monomer solution, this considerably increases the spacing between amination graphene oxide layer,
Advantageously account for dispersiveness, stability and homogeneous sex chromosome mosaicism of the particle in SPBI；Meanwhile the ammonia on amination graphene oxide
Base group can form corresponding chemical bond with the sulfonic acid group on SPBI, strengthen its interfacial interaction, uniform so as to obtain
Composite membrane.
The present invention specific preparation method be：
(1) preparation of amination graphene oxide
The alcohol dispersion liquid of graphene oxide, triethylene tetramine ultrasonic mixing is abundant, add N, N- dicyclohexyls carbon two
After imines and again progress ultrasonic disperse, 60 DEG C~120 DEG C return stirrings reactions, it is ultrasonically treated, filters, filter cake after the completion of reaction
Respectively washed 2~3 times with ethanol, deionized water, be dried in vacuo at last 60 DEG C~100 DEG C,
In dispersion liquid, the concentration of graphene oxide is 0.1~2mg/mL,
The ultrasonic time is respectively 1~5h, 1~5h, 0.5h three times,
The return stirring reaction time is 48h；
(2) preparation of high temperature resistant amination graphene oxide/sulfonate polybenzimidazole proton exchange composite membrane
The amination graphene oxide obtained in step (1) and polyphosphoric acids, phosphorus pentoxide are sufficiently mixed after 120
3h is stirred at DEG C；After being cooled to 50 DEG C, 3,3- diaminobenzidines are added, stirring 1h is maintained, adds 4,4- dicarboxyl hexichol
Ether, 5-sodium sulfo isophthalate, system temperature is risen into 90 DEG C of stirring 6h, 130 DEG C of stirring 11h, 160 DEG C of stirring 3h, 190
DEG C stirring 5h, then product is poured into deionized water, the thread product of obtained brown is immersed in 5wt.%Na2CO3In solution
48h, deionized water are washed till neutrality, 100 DEG C of 12~48h of vacuum drying, the product of gained are dissolved in into organic solvent, is made into quality point
Number is 5%~30% amination graphene oxide/sulfonate polybenzimidazole solution, after being film-made on a glass by knife coating,
150 DEG C of 12~48h of vacuum drying；The film of gained is immersed in the phosphoric acid solution of Solute mass concentration 50%~85% after drying
48h, it is washed with deionized after taking-up to neutrality, drying obtains amination graphene oxide/sulfonate polybenzimidazole proton and handed over
Change composite membrane,
Organic solvent is DMA, dimethyl sulfoxide (DMSO) or 1-METHYLPYRROLIDONE,
Main chemical reactions formula in step (2) is
The beneficial effects of the present invention are：From surface, amination graphene oxide and 3,3 '-diaminobenzidine
On all contain amino, both amino and hydroxy-acid group (4,4- dicarboxydiphenyl ethers, 5-sodium sulfo isophthalate) occur anti-
The probability answered should be suitable；But in the system of this programme, 3,3 '-diaminobenzidine but can perfect competition cross stone
Amino on black alkene, preferentially reacts with carboxyl, so as to protect the amino on graphene oxide to be used to improve stone well
The compatibility and formation acid-base pair of black alkene；
Protonation is realized after compound film bubble acid prepared by this patent, protonates the sulfonic acid group-SO in caudacoria3H (acidity)
With amino-NH2(alkalescence) can form the p- SO of soda acid3H…H2N-, respectively as proton donor and acceptor：Proton is from-SO3Solved on H
From making-SO3H dissociation turns into-SO3 -, now H2N-, which then receives proton, to be turned into+H3N-, subsequent-SO3 -Make upstream again+H3N- is solved
From by this way, proton transmits site by acid-base pair and transmitted, presence of the conductive process independent of water, in high temperature
Still there is good proton conductivity under dehydration even anhydrous state；
The PEM of the present invention is compared with the Nafion membrane of current commercial applications, and cost is low, and raw material sources are extensive,
Preparation method is simple, and amination graphene oxide spreads more evenly across in the polymer matrix, effectively improves composite proton exchange
Proton conductivity under the mechanical performance of film, heat endurance and high temperature.The made PEM of the present invention is in room temperature to 200 DEG C
In the range of all can be used, under the high temperature conditions, proton conduction property is excellent, has in terms of high temperature proton exchange film fuel cell
Good application prospect.
Brief description of the drawings
Fig. 1 is the embodiment of the present invention 2, embodiment 6, (dosage of 3,3- diaminobenzidines is comparative example 1
In 3.210g), SPBI and SPBI/GO-NH2Infrared spectrogram corresponding to composite membrane difference, as seen from the figure in 872cm-1、
1042cm-1And 1122cm-1Occur the characteristic peak of sulfonate radical at three, but mix GO-NH2Composite membrane afterwards and pure SPBI films phase
Than this characteristic peak at three is gradually reduced, and this is mainly SPBI/GO-NH2Formation-S=O ... H-N on the surface of composite membrane-
Key, this explanation composite film surface form soda acid proton pair, it was demonstrated that the presence of amino on amination graphene oxide.
Fig. 2 is that amination graphene oxide/sulfonate polybenzimidazole proton exchange composite membrane proton conductivity becomes with temperature
Change figure, (wherein, SPBI corresponds to embodiment 2, SPBI/GO-NH to its media thickness between 77 ± 5 μm2- 1 corresponding embodiment 5,
SPBI/GO-NH2- 2 corresponding embodiments 6, SPBI/GO-NH2- 3 corresponding implementations are 7).
Embodiment
Embodiment 1
The preparation of amination graphene oxide
200mL 1mg/mL graphene oxide ethanol solution is added first in dry three-necked flask, it is then molten at this
Triethylene tetramine is added in liquid, after ultrasonic 1h mixing fully, adds N, N- dicyclohexylcarbodiimides, ultrasonic 1h mixing is filled
Point, graphene oxide, triethylene tetramine, N, the weight ratio of N- dicyclohexylcarbodiimides is 1：25：150, three-necked flask is put
In digital display thermostatical oil bath, 60 DEG C of return stirrings react 48h, after the completion of reaction, ultrasonic 30min, then use polytetrafluoroethylene (PTFE)
Membrane filtration, filter cake is washed fully with ethanol, deionized water, and is dried to constant weight at 60 DEG C in vacuum drying chamber.
Embodiment 2
50g polyphosphoric acids, 5g phosphorus pentoxides are added in 100mL three-necked flasks, in N2Lower 120 DEG C of stirrings 3h is protected,
50 DEG C are then cooled to, 2.140g 3 is added, 3- diaminobenzidines, maintains stirring 1h；Add 1.298g 4,4- dicarboxyls two
Phenylate, 1.340g 5-sodium sulfo isophthalates, rise system temperature maintain to stir 6h to 90 DEG C, and 130 DEG C maintain stirring 11h,
160 DEG C maintain stirring 3h, and 190 DEG C maintain stirring 5h, then pour into product in deionized water, then by the thread production of obtained brown
Thing is immersed in 5wt.%Na2CO348h in solution, deionized water are washed till neutrality, 100 DEG C of vacuum drying 24h.The product of gained is molten
In DMA, the sulfonate polybenzimidazole solution that mass fraction is 5% is made into, 70 DEG C of heating 2h are subsequently placed at number
In aobvious thermostat water bath, after 60 DEG C of water-bath high-speed stirred 12h, it is film-made on a glass by knife coating, is put into 150 DEG C of vacuum and does
Taken out after dry case 48h, the film of gained is immersed into 48h in the phosphoric acid solution that mass fraction is 70%, is washed with deionized water after taking-up
Wash to neutrality, drying and obtain sulfonate polybenzimidazole proton exchange composite membrane.
Embodiment 3
Ammonia prepared by 50g polyphosphoric acids, 5g phosphorus pentoxides and 0.0048g embodiments 1 is added in 100mL three-necked flasks
Base graphene oxide, in N2Lower 120 DEG C of stirrings 3h is protected, 50 DEG C is then cooled to, adds 2.140g 3,3- benzidines
Amine, maintain stirring 1h；1.298g 4 is added, 4- dicarboxydiphenyl ethers, 1.340g 5-sodium sulfo isophthalates, raises system
Temperature maintains to stir 6h to 90 DEG C, and 130 DEG C maintain stirring 11h, and 160 DEG C maintain stirring 3h, 190 DEG C of maintenance stirring 5h, then will
Product is poured into deionized water, then the thread product of obtained brown is immersed in into 5wt.%Na2CO348h in solution, deionized water
It is washed till neutrality, 100 DEG C of vacuum drying 24h.The product of gained is dissolved in DMA, is made into mass fraction as 5%
Amination graphene oxide/sulfonate polybenzimidazole solution, 70 DEG C heating 2h be subsequently placed in digital display thermostat water bath, 60 DEG C
After water-bath high-speed stirred 12h, it is film-made by knife coating, is taken out after being put into 150 DEG C of vacuum drying chamber 48h on a glass, by institute
The film obtained immerses 48h in the phosphoric acid solution that mass fraction is 70%, is washed with deionized after taking-up to neutrality, drying and obtains ammonia
Base graphene oxide/sulfonate polybenzimidazole (mass ratio 0.1：99.9) proton exchange composite membrane.
Embodiment 4
Ammonia prepared by 50g polyphosphoric acids, 5g phosphorus pentoxides and 0.0239g embodiments 1 is added in 100mL three-necked flasks
Base graphene oxide, in N2Lower 120 DEG C of stirrings 3h is protected, 50 DEG C is then cooled to, adds 2.140g 3,3- benzidines
Amine, maintain stirring 1h；1.298g 4 is added, 4- dicarboxydiphenyl ethers, 1.340g 5-sodium sulfo isophthalates, raises system
Temperature maintains to stir 6h to 90 DEG C, and 130 DEG C maintain stirring 11h, and 160 DEG C maintain stirring 3h, 190 DEG C of maintenance stirring 5h, then will
Product is poured into deionized water, then the thread product of obtained brown is immersed in into 5wt.%Na2CO348h in solution, deionized water
It is washed till neutrality, 100 DEG C of vacuum drying 24h.The product of gained is dissolved in DMA, is made into mass fraction as 5%
Amination graphene oxide/sulfonate polybenzimidazole solution, 70 DEG C heating 2h be subsequently placed in digital display thermostat water bath, 60 DEG C
After water-bath high-speed stirred 12h, it is film-made by knife coating, is taken out after being put into 150 DEG C of vacuum drying chamber 48h on a glass, by institute
The film obtained immerses 48h in the phosphoric acid solution that mass fraction is 70%, is washed with deionized after taking-up to neutrality, drying and obtains ammonia
Base graphene oxide/sulfonate polybenzimidazole (mass ratio 0.5：99.5) proton exchange composite membrane.
Embodiment 5
Ammonia prepared by 50g polyphosphoric acids, 5g phosphorus pentoxides and 0.0478g embodiments 1 is added in 100mL three-necked flasks
Base graphene oxide, in N2Lower 120 DEG C of stirrings 3h is protected, 50 DEG C is then cooled to, adds 2.140g 3,3- benzidines
Amine, maintain stirring 1h；1.298g 4 is added, 4- dicarboxydiphenyl ethers, 1.340g 5-sodium sulfo isophthalates, raises system
Temperature maintains to stir 6h to 90 DEG C, and 130 DEG C maintain stirring 11h, and 160 DEG C maintain stirring 3h, 190 DEG C of maintenance stirring 5h, then will
Product is poured into deionized water, then the thread product of obtained brown is immersed in into 5wt.%Na2CO348h in solution, deionized water
It is washed till neutrality, 100 DEG C of vacuum drying 24h.The product of gained is dissolved in DMA, is made into mass fraction as 5%
Amination graphene oxide/sulfonate polybenzimidazole solution, 70 DEG C heating 2h be subsequently placed in digital display thermostat water bath, 60 DEG C
After water-bath high-speed stirred 12h, it is film-made by knife coating, is taken out after being put into 150 DEG C of vacuum drying chamber 48h on a glass, by institute
The film obtained immerses 48h in the phosphoric acid solution that mass fraction is 70%, is washed with deionized after taking-up to neutrality, drying and obtains ammonia
Base graphene oxide/sulfonate polybenzimidazole (mass ratio 1：99) proton exchange composite membrane.
Embodiment 6
Ammonia prepared by 50g polyphosphoric acids, 5g phosphorus pentoxides and 0.0956g embodiments 1 is added in 100mL three-necked flasks
Base graphene oxide, in N2Lower 120 DEG C of stirrings 3h is protected, 50 DEG C is then cooled to, adds 2.140g 3,3- benzidines
Amine, maintain stirring 1h；1.298g 4 is added, 4- dicarboxydiphenyl ethers, 1.340g 5-sodium sulfo isophthalates, raises system
Temperature maintains to stir 6h to 90 DEG C, and 130 DEG C maintain stirring 11h, and 160 DEG C maintain stirring 3h, 190 DEG C of maintenance stirring 5h, then will
Product is poured into deionized water, then the thread product of obtained brown is immersed in into 5wt.%Na2CO348h in solution, deionized water
It is washed till neutrality, 100 DEG C of vacuum drying 24h.The product of gained is dissolved in DMA, is made into mass fraction as 5%
Amination graphene oxide/sulfonate polybenzimidazole solution, 70 DEG C heating 2h be subsequently placed in digital display thermostat water bath, 60 DEG C
After water-bath high-speed stirred 12h, it is film-made by knife coating, is taken out after being put into 150 DEG C of vacuum drying chamber 48h on a glass, by institute
The film obtained immerses 48h in the phosphoric acid solution that mass fraction is 70%, is washed with deionized after taking-up to neutrality, drying and obtains ammonia
Base graphene oxide/sulfonate polybenzimidazole (mass ratio 2：98) proton exchange composite membrane.
Embodiment 7
Ammonia prepared by 50g polyphosphoric acids, 5g phosphorus pentoxides and 0.1433g embodiments 1 is added in 100mL three-necked flasks
Base graphene oxide, in N2Lower 120 DEG C of stirrings 3h is protected, 50 DEG C is then cooled to, adds 2.140g 3,3- benzidines
Amine, maintain stirring 1h；1.298g 4 is added, 4- dicarboxydiphenyl ethers, 1.340g 5-sodium sulfo isophthalates, raises system
Temperature maintains to stir 6h to 90 DEG C, and 130 DEG C maintain stirring 11h, and 160 DEG C maintain stirring 3h, 190 DEG C of maintenance stirring 5h, then will
Product is poured into deionized water, then the thread product of obtained brown is immersed in into 5wt.%Na2CO348h in solution, deionized water
It is washed till neutrality, 100 DEG C of vacuum drying 24h.The product of gained is dissolved in DMA, is made into mass fraction as 5%
Amination graphene oxide/sulfonate polybenzimidazole solution, 70 DEG C heating 2h be subsequently placed in digital display thermostat water bath, 60 DEG C
After water-bath high-speed stirred 12h, it is film-made by knife coating, is taken out after being put into 150 DEG C of vacuum drying chamber 48h on a glass, by institute
The film obtained immerses 48h in the phosphoric acid solution that mass fraction is 70%, is washed with deionized after taking-up to neutrality, drying and obtains ammonia
Base graphene oxide/sulfonate polybenzimidazole (mass ratio 3：97) proton exchange composite membrane.
Embodiment 8
Ammonia prepared by 50g polyphosphoric acids, 5g phosphorus pentoxides and 0.2389g embodiments 1 is added in 100mL three-necked flasks
Base graphene oxide, in N2Lower 120 DEG C of stirrings 3h is protected, 50 DEG C is then cooled to, adds 2.140g 3,3- benzidines
Amine, maintain stirring 1h；1.298g 4 is added, 4- dicarboxydiphenyl ethers, 1.340g 5-sodium sulfo isophthalates, raises system
Temperature maintains to stir 6h to 90 DEG C, and 130 DEG C maintain stirring 11h, and 160 DEG C maintain stirring 3h, 190 DEG C of maintenance stirring 5h, then will
Product is poured into deionized water, then the thread product of obtained brown is immersed in into 5wt.%Na2CO348h in solution, deionized water
It is washed till neutrality, 100 DEG C of vacuum drying 24h.The product of gained is dissolved in DMA, is made into mass fraction as 5%
Amination graphene oxide/sulfonate polybenzimidazole solution, 70 DEG C heating 2h be subsequently placed in digital display thermostat water bath, 60 DEG C
After water-bath high-speed stirred 12h, it is film-made by knife coating, is taken out after being put into 150 DEG C of vacuum drying chamber 48h on a glass, by institute
The film obtained immerses 48h in the phosphoric acid solution that mass fraction is 70%, is washed with deionized after taking-up to neutrality, drying and obtains ammonia
Base graphene oxide/sulfonate polybenzimidazole (mass ratio 5：95) proton exchange composite membrane.
Comparative example 1
On the basis of embodiment 6, by the dosage " 2.140g " of 3,3- diaminobenzidines be revised as successively " 3.210g ",
" 4.280g ", other operations are constant.
The detection of infrared spectrum and proton conductivity is carried out to the PEM prepared, find testing result with reality
The PEM applied in example 6 is consistent, illustrates that the situation that soda acid proton pair is formed in comparative example is also suitable with embodiment 6,
That is the amino and hydroxy-acid group (4,4- dicarboxyls two that the increase of 3,3- diaminobenzidines dosage is not had influence on graphene
Phenylate, 5-sodium sulfo isophthalate) probability that reacts, and in view of in embodiment 63,3 '-diaminobenzidine with
4,4- dicarboxydiphenyl ethers, the mol ratio of 5-sodium sulfo isophthalate sum are only 1：1, it can be concluded that in embodiment 6
3, the 3- diaminobenzidines of " 2.140g " dosage preferentially react with carboxyl, almost completely avoid on graphene
Amino participate in early stage polymerisation.
Claims (7)
1. a kind of preparation method of resistant to elevated temperatures amination graphene oxide/sulfonate polybenzimidazole proton exchange composite membrane, its
It is characterised by：The preparation method concretely comprises the following steps,
(1) preparation of amination graphene oxide
The alcohol dispersion liquid of graphene oxide, triethylene tetramine ultrasonic mixing is abundant, add N, N- dicyclohexylcarbodiimides
And return stirring reaction, it is ultrasonically treated, filters after the completion of reaction, be dried in vacuo after Washing of Filter Cake after progress ultrasonic disperse again；
(2) preparation of high temperature resistant amination graphene oxide/sulfonate polybenzimidazole proton exchange composite membrane
Stir, add after the amination graphene oxide obtained in step (1) is sufficiently mixed with polyphosphoric acids, phosphorus pentoxide
3,3- diaminobenzidines, 4,4- dicarboxydiphenyl ethers, 5-sodium sulfo isophthalate, system temperature is raised and stirred and is filled
Point, then product is poured into deionized water, the thread product of obtained brown is soaked into Na2CO3Solution, during deionized water is washed till
Property, dry, the product of gained is dissolved in into organic solvent is made into amination graphene oxide/sulfonate polybenzimidazole solution, passes through
After knife coating is film-made on a glass, the film of gained is immersed in acid solution after drying, is washed with deionized after taking-up into
Property, drying obtains amination graphene oxide/sulfonate polybenzimidazole proton exchange composite membrane.
2. the preparation method of proton exchange composite membrane as claimed in claim 1, it is characterised in that：In step (1), graphite oxide
The concentration of alkene is 0.1~2mg/mL.
3. the preparation method of proton exchange composite membrane as claimed in claim 1, it is characterised in that：In step (1), return stirring
React and be, 60 DEG C~120 DEG C return stirrings react 48h.
4. the preparation method of proton exchange composite membrane as claimed in claim 1, it is characterised in that：In step (2), by system temperature
Degree raise and stir sufficiently operation be, by system temperature rise to 90 DEG C stirring 6h, 130 DEG C stirring 11h, 160 DEG C stirring 3h,
190 DEG C of stirring 5h.
5. the preparation method of proton exchange composite membrane as claimed in claim 1, it is characterised in that：In step (2), by what is obtained
The thread product of brown is immersed in Na2CO3Time in solution is 48h.
6. the preparation method of proton exchange composite membrane as claimed in claim 1, it is characterised in that：Acid described in step (2)
Solution is the phosphoric acid solution of Solute mass concentration 50%~85%.
7. the preparation method of proton exchange composite membrane as claimed in claim 1, it is characterised in that：Having described in step (2)
Solvent is DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO) or 1-METHYLPYRROLIDONE.
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| CN108428918A (en) * | 2018-04-19 | 2018-08-21 | 温州市赢创新材料技术有限公司 | A kind of graphene sol proton membrane and preparation method thereof |
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| CN109293359A (en) * | 2018-08-31 | 2019-02-01 | 郭舒洋 | A kind of graphene metallic composite and preparation method thereof |
| CN109411796A (en) * | 2018-10-30 | 2019-03-01 | 成都市水泷头化工科技有限公司 | A kind of crosslinking proton exchange membrane and preparation method for vanadium cell |
| CN113699787A (en) * | 2021-08-18 | 2021-11-26 | 徐州蒙之禾塑料科技有限公司 | Antibacterial anti-static fiber coating and preparation method thereof |
| CN115746560A (en) * | 2022-10-20 | 2023-03-07 | 北京和瑞储能科技有限公司 | Amphiphilic alcohol self-assembly induced sulfonated polybenzimidazole ion exchange composite membrane and preparation method thereof |
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